CN1954024A - Self-adhesive prepreg - Google Patents
Self-adhesive prepreg Download PDFInfo
- Publication number
- CN1954024A CN1954024A CNA2005800152855A CN200580015285A CN1954024A CN 1954024 A CN1954024 A CN 1954024A CN A2005800152855 A CNA2005800152855 A CN A2005800152855A CN 200580015285 A CN200580015285 A CN 200580015285A CN 1954024 A CN1954024 A CN 1954024A
- Authority
- CN
- China
- Prior art keywords
- prepreg
- resin
- toughening agent
- thermoplasticity
- thermoplastic toughening
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000000853 adhesive Substances 0.000 title abstract description 20
- 229920005989 resin Polymers 0.000 claims abstract description 168
- 239000011347 resin Substances 0.000 claims abstract description 168
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 77
- 239000000203 mixture Substances 0.000 claims abstract description 73
- 239000000835 fiber Substances 0.000 claims abstract description 31
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 30
- 239000002131 composite material Substances 0.000 claims abstract description 11
- 239000004416 thermosoftening plastic Substances 0.000 claims description 75
- 239000012745 toughening agent Substances 0.000 claims description 74
- 239000004034 viscosity adjusting agent Substances 0.000 claims description 61
- 239000011159 matrix material Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 29
- 239000004593 Epoxy Substances 0.000 claims description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- 239000004695 Polyether sulfone Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- 229920006393 polyether sulfone Polymers 0.000 claims description 18
- 229920005649 polyetherethersulfone Polymers 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 14
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims description 12
- 239000002966 varnish Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 229920001971 elastomer Polymers 0.000 claims description 5
- 229920001721 polyimide Polymers 0.000 claims description 5
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 4
- 229930003836 cresol Natural products 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 229920003986 novolac Polymers 0.000 claims description 4
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 239000004642 Polyimide Substances 0.000 claims description 3
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 239000004643 cyanate ester Substances 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- XUCHXOAWJMEFLF-UHFFFAOYSA-N bisphenol F diglycidyl ether Chemical compound C1OC1COC(C=C1)=CC=C1CC(C=C1)=CC=C1OCC1CO1 XUCHXOAWJMEFLF-UHFFFAOYSA-N 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 2
- 229920006122 polyamide resin Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 239000009719 polyimide resin Substances 0.000 claims description 2
- 229920001021 polysulfide Polymers 0.000 claims description 2
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 2
- 239000011118 polyvinyl acetate Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims 2
- 150000001408 amides Chemical class 0.000 claims 1
- 229920000915 polyvinyl chloride Polymers 0.000 claims 1
- 238000012360 testing method Methods 0.000 description 26
- 239000012815 thermoplastic material Substances 0.000 description 22
- 239000010410 layer Substances 0.000 description 20
- 238000002360 preparation method Methods 0.000 description 12
- 230000001070 adhesive effect Effects 0.000 description 11
- 230000001413 cellular effect Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000013019 agitation Methods 0.000 description 8
- 230000000630 rising effect Effects 0.000 description 8
- 238000002156 mixing Methods 0.000 description 6
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 150000002118 epoxides Chemical class 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000004480 active ingredient Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920002492 poly(sulfone) Polymers 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920000271 Kevlar® Polymers 0.000 description 2
- 229920000784 Nomex Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 230000009172 bursting Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000004761 kevlar Substances 0.000 description 2
- 239000004763 nomex Substances 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000009194 climbing Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000007656 fracture toughness test Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- 235000009566 rice Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/10—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material
- B32B3/12—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material characterised by a layer of regularly- arranged cells, e.g. a honeycomb structure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24149—Honeycomb-like
- Y10T428/24157—Filled honeycomb cells [e.g., solid substance in cavities, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2369—Coating or impregnation improves elasticity, bendability, resiliency, flexibility, or shape retention of the fabric
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2926—Coated or impregnated inorganic fiber fabric
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2926—Coated or impregnated inorganic fiber fabric
- Y10T442/2984—Coated or impregnated carbon or carbonaceous fiber fabric
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
Abstract
Prepreg compositions comprised of fibers and a prepreg resin, comprising a thermosetting resin, a curing agent, and a plurality of thermoplastic polymers, in which greater than 10% of each of the thermoplastic polymers are soluble in the prepreg resin, are useful for making composite materials. In preferred embodiments, the prepreg compositions are used as self-adhesive prepregs for making honeycomb structures useful for various high performance applications.
Description
Technical field
The present invention relates to be used for preparing the composition of matrix material, in preferred embodiment, the present invention relates to can be used as the material of the used self-adhesive prepreg of the sandwich structure of preparation honeycomb-like sandwich structure and so on.
Background technology
Matrix material is widely used in having in the purposes of structure of high strength-to-weight ratio.These materials comprise the fortifying fibre (for example carbon or glass) in the embedded polymer thing substrate material (the normally thermosetting polymer of epoxy polymer and so on) usually.Matrix material normally by with matrix precursor (for example epoxide and solidifying agent) impregnation of fibers, forms " prepreg " and makes.Then prepreg is molded as required shape, and is cured, matrix precursor is converted into matrix material.
Can matrix material be made or be incorporated into structure according to required purposes with various size, shape and configuration.For example, sandwich structure is formed by the panel that is combined on the central layer opposite face usually.Conventional core material comprises rigid foam, paper, timber and honeycomb.Honeycomb is the vesicular structure that comprises the various materials of Nomex board fiber (available from DuPont) and/or aluminium and so on usually.Thin and the light sheet material that panel is normally made by the various materials that comprise matrix material.Owing to comprise that the honeycomb-like sandwich structure of composite panel has good strength-to-weight ratio and fatigue resistance usually, therefore be widely used in aerospace industry.Because the hole wall of cellular central layer is common and panel is a certain angle, so the contact area between hole wall edge and the panel is less.The tackiness agent that extends to contact area " fillet (fillet) " in addition along hole wall can be formed by using, the bonding strength between panel and the honeycomb can be increased.
Be used for the technology that cellular central layer combines with panel was just developed before a lot of years.For example, United States Patent (USP) the 3rd, 530, No. 087 (authorizing in 1970) disclosed and can be used to binder composition that panel is combined with cellular central layer.These binder compositions prepare by following steps: Resins, epoxy and polysulfone polymer are heated together, make the polysulfones dissolving, add solidifying agent, then the mixture that makes is made film.Mentioned in the literary composition and in tackiness agent, added fiber and metal powder filler.United States Patent (USP) the 3rd, 530, it is bonding with aluminum deck and porous aluminum central layer to have disclosed the use binder film No. 087.It is said that in tackiness agent adding polysulfones has improved bonded stripping strength between panel and the central layer.
In the time afterwards, developed the matrix material that comprises undissolved thermoplastic toughening agent in a large number.As described in United States Patent (USP) No. 4945154 (in the nineteen ninety mandate), it is believed that why thermoplastic material is in not dissolved state, be owing to can be combined in the amount of the thermoplastic material in the resinous substrates, be subjected to the processing characteristics of thermoplastic material to the gained thermosetting resin, the particularly restriction of viscosity and adhesive influence.According to United States Patent (USP) the 4th, 945, No. 154 described, and tackiness and mobile maintenance (or acceptable viscosity) often mean and can not use thermoplastic material it is believed that to reach under the necessary high capacity level of optimal mechanical character.Therefore, United States Patent (USP) the 4th, 945, disclosed for No. 154 polyethersulfone (PES) thermoplastic material has been dissolved in the resin, can reach far below the mechanical properties that it is believed that cured resin under the situation of the necessary content of optimization at PES content, greatly increase the viscosity of resin and reduce the tackiness of resin.Other the example that undissolved thermoplastic material is used for matrix material comprises United States Patent (USP) the 4th, 604, No. 319 (authorizing in 1986); The 4th, 957, No. 801 (authorizing) in nineteen ninety; With the 5th, 057, No. 353 (authorizing) in 1991, in these patents, thermoplastic material forms discontinuous layer in matrix material.Similarly, United States Patent (USP) the 5th, 169, No. 710 (authorizing in 1992) disclosed the matrix material of malleableize by adding polyamide granules; Equally referring to United States Patent (USP) the 6th, 045, No. 898 (authorizing) and the 6th, 429, No. 157 (in mandate in 2002 years) in 2000.General knowledge is, the thermoplastic toughening agent that is used for forming in the prepreg of matrix material also should be insoluble.
Developed in recent years and can make prepreg and the bonding self-adhesive prepreg of central layer not using under the situation of tackiness agent independently.For polynuclear plane, United States Patent (USP) the 6th, 440, No. 257 (authorizing in 2002) disclosed the dissolved thermoplastic granulates that any significance degree can not take place when being carried in the prepreg resin and formed particle as fillet, to form the prepreg autoadhesion, can not cause negative impact simultaneously to viscosity or other character of prepreg resin.In this solidification process, United States Patent (USP) the 6th, 440 has disclosed fillet for No. 257 and has formed particulate and dissolve gradually and make resin viscosity increase gradually, and this has promoted the formation of fillet.Therefore, general knowledge thinks that still any significant dissolving should not take place the thermoplastic toughening agent in the prepreg.
Summary of the invention
Opposite with general knowledge, we have found to comprise the prepreg composition of thermoplastic toughening agent amazedly, and wherein thermoplastic toughening agent at room temperature is dissolved in the middle of the prepreg resin fully or fully.Can handle preferred prepreg composition by many kinds of manufacturing technologies that comprise manual laying and automatization shop band and so on, make it form matrix material.The matrix material that makes can be incorporated in the various composite structures, comprise the main and secondary structure of aircraft.In preferred embodiment, described prepreg composition is suitable as the used self-adhesive prepreg of preparation honeycomb-like sandwich structure.
The prepreg composition preferred embodiment is provided, and said composition comprises at least one layer of fibers that is impregnated with the prepreg resin; Described prepreg resin comprises thermosetting resin, solidifying agent, thermoplasticity viscosity modifier and thermoplastic toughening agent, gross weight in the prepreg resin is a benchmark, and the total amount of described thermoplasticity viscosity modifier and thermoplastic toughening agent is about 25-40 weight %; Be benchmark in thermoplasticity viscosity modifier and thermoplastic toughening agent gross weight separately, record respectively have 10 weight % above thermoplasticity viscosity modifier and thermoplastic toughening agent to dissolve in the prepreg resin respectively at about 25 ℃; Be under 2 ℃/minute the condition, net phase prepreg resin sample to be recorded in heating rate, the minimal viscosity of prepreg resin is about the 25-1500 pool.
Another preferred embodiment provides a kind of composite structure, and this composite structure comprises by solidifying the matrix material that above-mentioned prepreg composition makes.Preferably, described composite structure is the form of honeycomb-like sandwich structure.
Another preferred embodiment provides a kind of preparation prepreg method for compositions, and this method comprises: form the prepreg resin comprise thermosetting resin, optional solidifying agent, thermoplasticity viscosity modifier and thermoplastic toughening agent; Gross weight in net phase prepreg resin sample is a benchmark, and the total content of thermoplasticity viscosity modifier and thermoplastic toughening agent is about 25-40 weight %; Be benchmark in thermoplasticity viscosity modifier and thermoplastic toughening agent gross weight separately, record respectively have 10 weight % above thermoplasticity viscosity modifier and thermoplastic toughening agent to dissolve in the prepreg resin respectively at about 25 ℃; Be under 2 ℃/minute the condition, net phase prepreg resin sample to be recorded in heating rate, the minimal viscosity of prepreg resin is about the 25-1500 pool; And a large amount of fibers are contacted with the prepreg resin.
The present invention also provides the resin of the homogeneous phase with controlled minimum viscosity.This resin is applicable to abundant dipping prepreg, is applicable to that also cutting the film bar uses and the resin impregnation technology.These embodiments and other embodiments have been described hereinafter in more detail.
Description of drawings
By the following description and drawings, all respects of the present invention are conspicuous, and these are described and accompanying drawing only is to be used for illustrating of the present invention, the present invention are not construed as limiting.
Fig. 1 is in the preferred implementation of prepreg resin of the present invention, under 1 ℃/minute temperature rise rate, and the Rheological Study curve of viscosity with temperature variation relation.
Fig. 2 is in the preferred implementation of prepreg resin of the present invention, under 2 ℃/minute temperature rise rate, and the Rheological Study curve of viscosity with temperature variation relation.
Fig. 3 is in the preferred implementation of prepreg resin of the present invention, under 5 ℃/minute temperature rise rate, and the Rheological Study curve of viscosity with temperature variation relation.
Fig. 4 is in the preferred implementation of prepreg resin of the present invention, under 10 ℃/minute temperature rise rate, and the Rheological Study curve of viscosity with temperature variation relation.
Embodiment
Prepreg composition (comprising the layer of fibers that at least one has flooded the prepreg resin) preferred embodiment is provided, preparation prepreg method for compositions (comprise fiber is contacted with the prepreg resin), the matrix material that forms by described prepreg composition, and the composite structure that comprises described matrix material.Preferred prepreg composition is fit to be used for make many kinds of composite structures (main and secondary structure and the sports equipment that comprise aircraft) by various manufacture method, and described manufacture method comprises manual laying and automatization shop band (ATL).Especially preferably be fit to be used for making the self-adhesive prepreg composition of honeycomb-like sandwich structure.
Preferred prepreg composition comprises at least one layer of fibers with the prepreg resin impregnation.Be applicable to that fiber in the prepreg comprises glass fibre, synthetic polymeric fibers (for example available from DuPont Kevlar Kevlar), ceramic fiber, carbon fiber, silica fiber, polyethylene fibre, boron fibre or their mixture.Described fiber can be a various forms, for example filament tow, no latitude band or fabric.Many suitable fibers can be buied on market.
Preferred prepreg resin comprises thermosetting resin, solidifying agent, thermoplasticity viscosity modifier and thermoplastic toughening agent.Many thermosetting resins can be buied on market, and/or well known by persons skilled in the art, can select according to the function of gained solidified matrix material expection.At United States Patent (USP) the 6th, 440, thermosetting resin and examples of applications thereof have been described in No. 257, this full patent texts is incorporated by reference into herein.The example of preferred thermosetting resin comprises Resins, epoxy, cyanate ester resin, polyamide resin and polyimide resin (for example bismaleimides).Preferred Resins, epoxy comprises triglycidyl ether, epoxy phenol phenolic varnish, cresol novolac epoxy varnish and the N of bisphenol-f-diglycidylether, bisphenol-A-diglycidylether, p-aminophenol, N, N ', N '-four glycidyl group-4,4-methylenedianiline.Preferably, described thermosetting resin comprises the main chain functional group similar and/or compatible with the main chain functional group of thermoplasticity viscosity modifier.
Usually use solidifying agent, make thermosetting resin cured (often by the heating accelerated reaction) by chemical reaction.Described thermosetting resin is preferably as matrix precursor, and when solidifying under the situation of the fiber that is scattered here and there therein, this precursor conversion is a polymeric matrix.Preferably according to the well-known principle of those skilled in the art, be used for the kind and the amount of cured thermosetting based on solidifying agent, select the kind and the amount of solidifying agent.Described solidifying agent can become the part (for example the epoxide group reaction of the usually amino and Resins, epoxy of amine hardener forms chemical bonding) of the structure of solidified resin, and perhaps described solidifying agent can be used as catalyzer.At United States Patent (USP) the 6th, 440, disclosed the example of various solidifying agent in No. 257, this patent reference is incorporated into this paper, is used for describing solidifying agent and application thereof.Amine is preferably to be used for curing agent for epoxy resin.The example of preferred amine hardener comprises 4,4 '-diamino diphenyl sulfone, Dyhard RU 100 and their mixture.
Opposite with general knowledge, thermoplasticity viscosity modifier of the present invention and thermoplastic toughening agent preferably fully or fully are dissolved in the prepreg resin.Gross weight in thermoplasticity viscosity modifier in the prepreg resin is a benchmark, record at about 25 ℃, preferably surpass 10 weight %, dissolve in the prepreg resin more preferably about the thermoplasticity viscosity modifier that surpasses 20 weight %, more preferably from about surpasses 50 weight %.Best is that under about 25 ℃, virtually all thermoplasticity viscosity modifier all dissolves in the prepreg resin.
Described thermoplasticity viscosity modifier can be selected from various thermoplastic materials.Be preferably based on solvability and the kind of the thermosetting resin in the prepreg resin and the kind and the amount that content is selected the thermoplasticity viscosity modifier of thermoplasticity viscosity modifier.The example of preferred thermoplasticity viscosity modifier comprises polyhydroxy ether, polyethers, polyethersulfone, polyether ethersulfone, polyethersulfone/polyether ethersulfone multipolymer, polysulphide, cresols phenolic varnish, phenol phenolic varnish, cresol novolac epoxy varnish, epoxy phenol phenolic varnish, polyvinyl butyral acetal (PVB), polyvinyl chloride (PVC), polyvinyl alcohol, polyvinyl acetate, polyvinyl formal (PVF), the rubber that contains vinyl cyanide and polyimide.Preferably, described thermoplasticity viscosity modifier comprises the main chain functional group similar and/or compatible to the main chain functional group of thermosetting resin.Therefore, for example polyhydroxy ether is the thermoplasticity viscosity modifier that preferably is used for the epoxy type thermosetting resin.The polyhydroxy ether (available from PhenoxyResins) of commodity PKHB-100 by name is particularly preferred thermoplasticity viscosity modifier.
The thermoplasticity viscosity modifier is a kind of thermoplastic material, and its content in the prepreg resin is compared with the comparable prepreg resin that comprises more a spot of this thermoplastic material, can increase the viscosity of net phase (solvent-free) prepreg resin.
Preferably, the content of thermoplasticity viscosity modifier makes the minimal viscosity of prepreg resin be about the 25-1500 pool in the prepreg resin, more preferably about being the 25-250 pool, be more preferably the 40-75 pool, described viscosity is to use rheometer, under the condition of 2 ℃/minute of frequency 10 radian per seconds, strain 50%, heating rate, on net phase (solvent-free) prepreg resin sample, record.
Fig. 1-4 has shown the rheological of sample under following four kinds of temperature rise rates according to the preferred implementation of the prepreg resin of the present invention of formation as described in embodiment 1: 1 ℃/minute; 2 ℃/minute; 5 ℃/minute; 10 ℃/minute.These figure have shown in the process with illustrated various heating rate heating prepreg resins, the viscosity under all temps (Eta).Preferred heating rate is 2 ℃/minute, therefore uses 2 ℃/minute heating rate that the preferred viscosity characteristics of prepreg resin of the present invention is described.The minimal viscosity that prescription of the present invention except embodiment 1 will influence in the heat-processed to be reached.
The amount of thermoplasticity viscosity modifier and the degree that net phase prepreg resin viscosity is increased thereof are tended to change according to the kind and the molecular weight thereof of thermoplastic material.Gross weight in the prepreg resin is a benchmark, and the content of the thermoplasticity viscosity modifier in the prepreg resin is about 0.5-15 weight % usually, is more preferably 1-10 weight %, but also can adopts greater or lesser consumption sometimes.The effectiveness of thermoplasticity viscosity modifier is tended to change with its molecular weight, is therefore waiting under the weight situation, and the thermoplastic material of higher molecular weight makes degree that viscosity increases usually greater than the thermoplastic material of lower molecular weight.Preferably, the number-average molecular weight Mn of thermoplasticity viscosity modifier (unit is dalton) is about 9,000-16, and 000, be more preferably 9,000-11,000.The soltion viscosity that records the thermoplasticity viscosity modifier in 25 ℃ 20% cyclohexane solution preferably is about the 180-900 centipoise, is more preferably the 175-425 centipoise.
Described thermoplastic toughening agent preferably also is dissolved in the prepreg resin fully or fully.Thermoplastic toughening agent is a kind of thermoplastic material, and its content in the prepreg resin is compared with the comparable matrix material that comprises more a spot of this thermoplastic material, can increase the toughness by the matrix material of described prepreg preparation of compositions.Toughness can be called the 1 type fracture toughness test mensuration of GlC by Boeing Standard Method BSS 7260 (impacting back compression (CAI) test) or those skilled in the art.Gross weight in the thermoplastic toughening agent in the prepreg resin is a benchmark, preferably, record at about 25 ℃, surpass 10 weight %, dissolve in the prepreg resin more preferably about the thermoplastic toughening agent that surpasses 20 weight %, more preferably from about surpasses 50 weight %.Best is that under about 25 ℃, virtually all thermoplastic toughening agent all dissolves in the prepreg resin.Described thermoplasticity viscosity modifier and the solvability of thermoplastic toughening agent in prepreg can be measured with the opticmicroscope of 300 times of amplifications under 25 ℃.Therefore, if under 25 ℃, use the opticmicroscope of 300 times of amplifications in the prepreg resin, to observe the particle of thermoplasticity viscosity modifier and thermoplastic toughening agent, think that then these particles are insoluble.
The amount of thermoplastic toughening agent with and the degree that makes the toughness of matrix material of gained increase tend to change according to the kind and the molecular weight thereof of thermoplastic material.Gross weight in the prepreg resin is a benchmark, and the amount of thermoplastic toughening agent is about 20-35 weight % in the prepreg resin usually, is more preferably 25-30 weight %, but also can adopts more or less consumption sometimes.The effectiveness of thermoplastic toughening agent is tended to change along with its molecular weight, makes under equiponderant situation, and the thermoplastic material of higher molecular weight makes the thermoplastic material of the degree of toughness increase greater than lower molecular weight.Preferably, the number-average molecular weight Mn of thermoplastic toughening agent is about 6,000-12, and 000, be more preferably 9,000-12,000.
Described thermoplastic toughening agent is optional takes pride in multiple thermoplastic material.To the selection of the kind of thermoplastic toughening agent and the consumption toughness when the dissolution characteristics of the kind of thermosetting resin in the prepreg resin and content, thermoplastic material and thermoplastic material be not in being incorporated into matrix material preferably.United States Patent (USP) the 6th, 437, No. 080 full text is incorporated by reference into herein, is used for specifically describing the thermoplastic material that can be used as thermoplastic toughening agent.Polyethersulfone, polyether ethersulfone and their multipolymer are the examples of preferred thermoplastic toughening agent.At United States Patent (USP) the 6th, 437, polyethersulfone/polyether ethersulfone (PES/PEES) multipolymer of describing among No. 080 the work embodiment is particularly preferred thermoplastic toughening agent.
Gross weight in the prepreg resin is a benchmark, and the total amount of thermoplasticity viscosity modifier and thermoplastic toughening agent preferably is about 25-40 weight % in the prepreg resin, is more preferably 30-35 weight %.The classification of this paper is not the mutual exclusion exclusiveness, this is because the thermoplasticity viscosity modifier may have the malleableize effect, the possible increased viscosity of thermoplastic toughening agent, but in special arbitrarily prepreg resin, the thermoplasticity viscosity modifier is different from thermoplastic toughening agent.
The prepreg resin can comprise one or more other additive well known by persons skilled in the art, for example inorganic particle, tinting material, stablizer, catalyzer, fire retardants etc.Substantially do not contain the thermoplasticity fillet that can't fully be dissolved in the prepreg resin in the preferred prepreg resin and form particle, for example United States Patent (USP) the 6th, 440, the prepreg resin described in No. 257.
Can prepare the prepreg resin by thermosetting resin, solidifying agent, thermoplasticity viscosity modifier and thermoplastic toughening agent and any other optional additives are mixed with random order.Preferably, also solvent is mixed mutually with said components, to promote good mixing and homogeneity.The selection of solvent types and consumption is preferably carried out based on the kind of component in the prepreg resin and consumption.Preferably, use sufficient amount of solvent, to make basic prepreg resin combination uniformly with the whole component of basic dissolving.The described prepreg resin that comprises solvent can be used to impregnation of fibers, perhaps can (perhaps solvent be evaporated from the prepreg resin substantially fully and remove by the part evaporating solvent, prepreg resin with the preparation net phase), the prepreg resin of gained is used for impregnation of fibers.The example of suitable solvent comprises methylene dichloride, dimethyl formamide, tetrahydrofuran (THF) and preferred acetone, methyl ethyl ketone and 1,3-dioxolane.
Also can thermosetting resin, solidifying agent, thermoplasticity viscosity modifier and thermoplastic toughening agent and any other optional additive be mixed the prepreg resin for preparing net phase in any order by under not solvent-laden condition.Be to be understood that one or more active ingredients can be used as the solvent of one or more other active ingredients, but in this article, these active ingredients do not represented in term " solvent ".Component is preferably carried out under the condition of heating in the mixing under the not solvent-laden condition, and more preferably this mixing divides a plurality of stages to carry out.For example, one preferred embodiment in, in the fs, by with first part's thermoplastic toughening agent and part or all of at least a other component (thermosetting resin of at least a portion for example, and/or at least a portion, more preferably whole thermoplasticity viscosity modifier) mix, form premixture, this time mixing is preferably carried out under heating condition, more preferably is heated to be approximately higher than 40 ℃.Preferably, the thermoplastic toughening agent and the thermoplasticity viscosity modifier of most of or whole basically first parts all dissolve in this premixture basically.Preferably, described premixture does not contain solidifying agent, and making can be at comparatively high temps with than mixing better under the low viscosity, and premature curing can not take place.
Then this premixture is mixed mutually with the remaining part of other parts and/or other components of the toughner of second section and optional toughner (for example thermosetting resin, any remaining part of solidifying agent and/or thermoplasticity viscosity modifier) at least.The second section of described thermoplastic toughening agent can be chosen wantonly and comprise the thermoplastic toughening agent particle, and for example number average particle size is the particle of 60-150 micron.For the undissolved mixing condition of thermoplastic toughening agent particle that is added, gross weight in thermoplastic toughening agent in the gained prepreg resin is a benchmark, record under about 25 ℃, the relative quantity of thermoplastic toughening agent preferably makes greater than 10 weight %, more preferably about greater than 25 weight %, more preferably from about the thermoplastic toughening agent greater than 50 weight % dissolves in the prepreg resin of gained in described first part and the second section.
The prepreg composition is preferably by with prepreg resin impregnation or " preimpregnation " fiber (for example by a large amount of fibers is contacted with the prepreg resin, making independent fiber suitably well be applied by the prepreg resin) and form.The various methods that fiber is contacted with the prepreg resin are well known by persons skilled in the art, comprise solution method and body method mutually.For example, in a preferred embodiment, the fiber that makes no latitude band or Woven fabric form is by comprising the bath of prepreg resin.Mechanical treatment (for example making the prepreg composition by a pair of roller with predetermined gap) can be carried out then to the prepreg composition (comprising fiber and prepreg resin) of gained, to remove any excessive prepreg resin.Usually make solvent evaporation arbitrarily, the prepreg composition is evaporated with promotion by drying oven.Final prepreg composition does not preferably contain solvent substantially, in the prepreg composition total weight, preferably comprises about 35-45 weight %, more preferably the prepreg resin of about 38-42 weight %.
Matrix material can pass through method known to those skilled in the art, is made by the prepreg composition.For example, one preferred embodiment in, a pair of double-deck carbon fibre initial rinse stain body is stacked up, form a pair of prepreg face, under the situation of not using tackiness agent, it is applied to the opposite face (+45,0/90 of the cellular central layer of Nomex then, core, 0/90 ,+45).With the pack of the structure for vacuum of gained, use Boeing BMS 8-256 in autoclave then, under 350 , solidified 2 hours, forming honeycomb-like sandwich structure, heating rate be about 1-5 /minute.The rising roller is peeled off test (climbing drum peel test) (ASTMD 1781) and is found panel and cellular central layer good combination, the microscopic inspection of example cross section is found to form suitable fillet, and required flowing taken place in this explanation prepreg resin in solidification process.Back compression (CAI) is tested and the test of 1 type fracture toughness property (GlC) records by duplexer is impacted, and the preferred honeycomb-like sandwich structure and the duplexer that use prepreg composition as herein described to make also have splendid toughness.
Prepared the prepreg resin by following steps: by under about 90 ℃ heating, the diglycidyl (trade(brand)name MY 0510) of 12.4 gram bisphenol-f-diglycidylethers (trade(brand)name PY 306) and 37.2 gram p-aminophenol is mixed, made the thermosetting resin that comprises epoxy resin composition.The thermoplastic toughening agent of first part (14.1 gram number-average molecular weights are about 40: 60 polyethersulfone/polyether ethersulfone multipolymer of 11000, according to United States Patent (USP) the 6th, 437, No. 080 described preparation) is added in the mixture of Resins, epoxy lentamente.Also thermoplasticity viscosity modifier (5.04 gram polyhydroxy ethers, trade(brand)name PKHB-100) is added in the mixture of Resins, epoxy.The mixture of gained all dissolves until thermoplastic toughening agent and thermoplasticity viscosity modifier in about 90 ℃ of heating.Mixture with gained is cooled to about 40-50 ℃ then, adds about 40 gram acetone, forms strong solution.Under about 40-50 ℃ temperature, under agitation the thermoplastic toughening agent (the above-mentioned polyethersulfone/polyether ethersulfone multipolymer of 14.1 grams) with second section adds in this strong solution, until thermoplastic toughening agent dissolving (about 30 minutes) then.In solution, add solidifying agent (15.7 grams 4,4 '-mixture of diamino diphenyl sulfone and 1.38 gram Dyhard RU 100s) then, form the prepreg resin.
Embodiment 2
Prepared the prepreg resin by following steps: by under about 90 ℃ heating, the triglycidyl ether (trade(brand)name MY 0510) of 12.4 gram bisphenol-f-diglycidylethers (trade(brand)name PY 306) and 37.2 gram p-aminophenol is mixed, made the thermosetting resin that comprises epoxy resin composition.Whole thermoplastic toughening agent (described 40: the 60 polyethersulfone/polyether ethersulfone multipolymer of 28.2 gram embodiment 1) is added in the mixture of Resins, epoxy lentamente.Also thermoplasticity viscosity modifier (5.04 gram polyhydroxy ethers, trade(brand)name PKHB-100) is added in the mixture of Resins, epoxy.The mixture of gained all dissolves until thermoplastic toughening agent and thermoplasticity viscosity modifier in about 90 ℃ of heating.Mixture with gained is cooled to about 40-50 ℃ then, adds about 40 gram acetone, forms strong solution.In solution, add solidifying agent (15.7 grams 4,4 '-mixture of diamino diphenyl sulfone and 1.38 gram Dyhard RU 100s) then, form the prepreg resin.
Embodiment 3
Prepared the prepreg composition by following steps: make weight be 190-200 gram/square metre plain weave carbon fabric (comprising the carbon fiber that T300 3 K never twist) with about 1-5 rice/minute the prepreg resin of speed by preparation as described in top embodiment 1, then by approximately remaining on 80-120 ℃ baking oven, with the evaporation acetone solvent.Adopt dipping and flow process or roll spacing to make the prepreg resin of textile impregnation aequum.Gross weight in the prepreg composition is a benchmark, and the prepreg composition of gained comprises the prepreg resin of about 38-42 weight %.
By in press, the prepreg composition being suppressed, made the sample of prepreg resin by the prepreg composition.Detect the prepreg resin sample at 25 ℃ by opticmicroscope (300 times).Do not observe the particle of thermoplasticity viscosity modifier or thermoplastic toughening agent, this illustrates that virtually all thermoplasticity viscosity modifier and thermoplastic toughening agent all dissolve in the prepreg resin.
Embodiment 4
Prepare the prepreg resin by following steps: by (20 restrain bisphenol-f-diglycidylethers with thermosetting resin, trade(brand)name PY 306) (5.04 restrain polyhydroxy ethers with the thermoplastic toughening agent of first part (embodiment 1 described 7.1 gram polyethersulfone/polyether ethersulfone multipolymers) and thermoplasticity viscosity modifier, trade(brand)name PKHB-100) mixes, make premixture.The gained mixture under agitation heats under about 90-130 ℃, with dissolving first part's thermoplastic toughening agent and thermoplasticity viscosity modifier.Premixture with gained is cooled to about 40-50 ℃ then, under agitation adds the thermosetting resin (diglycidylether that comprises 5.4 gram bisphenol-f-diglycidylethers and 25.0 gram p-aminophenol) of other part and the thermoplastic toughening agent (21.1 gram above-mentioned polyethersulfone/polyether ethersulfone multipolymer) of second section.Under agitation add solidifying agent (15.7 grams 4,4 '-mixture of diamino diphenyl sulfone and 1.38 gram Dyhard RU 100s) then to form the prepreg resin.
Embodiment 5
Prepare the prepreg resin by following steps: by hybrid thermosetting resin (10.8 gram bisphenol-f-diglycidylethers, trade(brand)name PY 306) and (triglycidyl ether of 36.4 gram p-aminophenol, trade(brand)name MY0510) and thermoplastic toughening agent (28.2 gram embodiment 1 described polyethersulfone/polyether ethersulfone multipolymer) and thermoplasticity viscosity modifier (5.04 restrain polyhydroxy ethers, trade(brand)name PKHB-100), prepared premixture.The mixture of gained approximately under 90-130 ℃, heating under agitation, with dissolving thermoplastic toughening agent and thermoplasticity viscosity modifier.Premixture with gained is cooled to about 40 ℃-50 ℃ then, under agitation adds about 5 grams 1 in mixture, the 3-dioxolane.Under agitation in mixture, add then solidifying agent (15.7 the gram 4,4 '-diamino diphenyl sulfone).Under agitation add catalyzer (1.50 gram bisphenol-f-diglycidylethers, the mixture of trade(brand)name PY 306 and 1.50 gram Dyhard RU 100s) then, to form the prepreg resin.
Embodiment 6
According to being used for making the standard step of carrying out the used structure of mechanical test described in following examples 8, use prepreg preparation of compositions honeycomb-like sandwich structure and sample as preparation as described in the embodiment 3.
Comparative example 7
Use step similar to Example 3 to prepare reference prepreg composition, be with the difference of embodiment 3, described prepreg resin is the Resins, epoxy of succinonitrile (CTBN) the rubber improvement that is applicable to the carboxy blocking of aircraft secondary structure at present.Cellular interlayer reference structure is to use reference prepreg composition, makes by the step that is used for making the used structure of ASTM D 1781 (the rising roller is peeled off) test.Make two groups of reference structures, one group is used film adhesive (epoxide that is different from the CTBN modified rubber of matrix) that cellular central layer and panel is bonding, and another group is not used film adhesive.The cellular interlayer reference structure of described use film adhesive can be used for the aircraft secondary structure at present.
Table 1 has shown the rising roller stripping test data that two groups of structures are recorded.Testing data shows that film adhesive has significantly improved the mechanical properties of honeycomb-like sandwich structure, removes film adhesive and can make mechanical properties that disadvantageous reduction takes place from the material that is suitable at present.
Table 1
| Test | Reference CTBN epoxy substrate (not using film adhesive) | Reference CTBN epoxy substrate (use film adhesive) | ||
| The rising roller is peeled off (room temperature, 0 day) | Tool-face (in-lb/3 inch) | Bag face (in-lb/3 inch) | Tool-face (in-lb/3 inch) | Bag face (in-lb/3 inch) |
| 9-11 | 8-12 | 24-27 | 26-28 | |
Embodiment 8
Honeycomb-like sandwich structure and sample according to the described preparation of embodiment 4-5 are carried out following mechanical test, and those skilled in the art often adopt these mechanical tests to determine that structure has the required mechanical properties of specific end use:
The rising roller is peeled off (ASTM D 1781): this test is commonly used to measure the bond strength on panel and cellular central layer surface.The flexible bigger panel of this thermometrically sandwich structure and the antistripping ability of the adhering junction between the central layer.This test is mainly used to estimate the structure that is used for the application of commercial aircraft secondary structure.
Stock deflection (Long Beam Flex) (ASTM C 393-94): this test is commonly used to characterize the mechanical properties of smooth sandwich structure, make this sandwich structure crooked under the situation of keeping flat in some way, the moment that applies that causes the sandwich panel bending makes top panel generation compressive failure, bottom panel generation tensile fracture.This test is mainly used to estimate the structure that is used for the application of commercial aircraft secondary structure.
Horizontal drawing (Flatwise Tension) (ASTM C 297-94): this test is commonly used to characterize the horizontal drawing tensile strength of central layer, or bonded intensity between the central layer of the sandwich plate of combination and the panel.This test comprises sandwich plate is applied tensile loading perpendicular to this plate plane that this load is by being passed to the interlayer framework with the thick load piece of sandwich panel bonded (thick loading block).This test is mainly used to estimate the structure that is used for the application of commercial aircraft secondary structure.
Impact back compression (CAI, Boeing Standard Method BSS 7260): this test is commonly used to characterize with after this structure of particular energy strength impact, the compressive strength of structure.After the impact, this structure is compressed the effect of load under low homogeneous strain rate.This test provides about resin system flexible data.This test is mainly used to estimate the structure that is used for the application of commercial aircraft primary structure.
GlC: this test is used between the flaggy of crackle trigger in the solidified duplexer usually and is caused bursting form, to characterize the shear property of matrix.With 1 type bursting form the flaggy stretching is separated.This test provides about resin system flexible data.This test is mainly used to estimate the structure that is used for the application of commercial aircraft primary structure.
Table 2 show to use the honeycomb-like sandwich structure that embodiment 6 described self-adhesive prepregs make and the test data of sample, and a series of data that comprise the reference structure of CTBN modified rubber epoxide substrate that prepare with embodiment 5 described film adhesives.As described in embodiment 7, film adhesive makes the mechanical properties of reference structure be better than not using the structure of film adhesive, and these mechanical propertiess are enough to be used in the secondary structure of aircraft.
Data declaration in the table 2 can satisfy consumption standard according to the honeycomb-like sandwich structure and the sample of preparation described herein, also surpasses the performance of reference product in some cases, and particularly the toughness when resin system has under the situation of importance.Benefit for manufacturers comprises minimizing labour cost and material cost, also weight reduction (increase strength/weight).
Table 2
| Test | Self-adhesive prepreg | Reference | ||
| Stock deflection (accurate 2 layers) | Load (pound) | P/Y pound/inch | Load (pound) | P/Y pound/inch |
| 250-260 | 170-185 | 260-275 | 160-170 | |
| The stock deflection (accurate 2 layers, 200 , wet) | Load (pound) | P/Y pound/inch | Load (pound) | P/Y pound/inch |
| 185-195 | 160-170 | 175-185 | 140-150 | |
| The rising roller is peeled off (room temperature 0 day) | Tool-face (in-lb/3 inch) | Bag face (in-lb/3 inch) | Tool-face (in-lb/3 inch) | Bag face (in-lb/3 inch) |
| 24-27 | 22-25 | 24-27 | 26-28 | |
| The rising roller is peeled off (10 day separation time of room temperature) | Tool-face (in-lb/3 inch) | Bag face (in-lb/3 inch) | Tool-face (in-lb/3 inch) | Bag face (in-lb/3 inch) |
| 22-23 | 23-25 | 24-28 | 27-28 | |
| The rising roller is peeled off (160 /wet) | Tool-face (in-lb/3 inch) | Bag face (in-lb/3 inch) | Tool-face (in-lb/3 inch) | Bag face (in-lb/3 inch) |
| 24-26 | 22-25 | 27-29 | 25-27 | |
| Horizontal drawing (envrionment conditions) | Intensity (psi) | Intensity (psi) | ||
| 775-790 | 770-780 | |||
| GlC | Inch * pound/inch 2 | Inch * pound/inch 2 | ||
| 5.9-6.3 | 2.2-2.6 | |||
| Impact the back compression | Intensity (ksi) | Intensity (ksi) | ||
| 40-43 | 26-28 | |||
All reference mentioned in this article and patent all are incorporated by reference into this paper in full.Although below invention has been described in conjunction with some preferred implementation, consider the content that this paper discloses, other embodiment is conspicuous to those of ordinary skills.Therefore scope of the present invention is not limited to the content of preferred implementation.
Claims (25)
1. prepreg composition, said composition comprise at least one layer of fibers with the prepreg resin impregnation;
Described prepreg resin comprises thermosetting resin, solidifying agent, thermoplasticity viscosity modifier and thermoplastic toughening agent, gross weight in the prepreg resin is a benchmark, and the total amount of described thermoplasticity viscosity modifier and thermoplastic toughening agent is about 25-40 weight %;
Wherein, be benchmark in thermoplasticity viscosity modifier and thermoplastic toughening agent gross weight separately respectively, record at about 25 ℃, respectively there are the thermoplasticity viscosity modifier and the thermoplastic toughening agent that surpass 10 weight % to dissolve in the prepreg resin; And
Be under 2 ℃/minute the condition, net phase prepreg resin sample to be recorded in heating rate, the minimal viscosity of prepreg resin is about the 25-1500 pool.
2. prepreg composition as claimed in claim 1 is characterized in that, described minimal viscosity is about the 25-250 pool.
3. prepreg composition as claimed in claim 1 is characterized in that, all basically thermoplasticity viscosity modifiers all dissolve in the prepreg resin.
4. prepreg composition as claimed in claim 1 is characterized in that, dissolves in the prepreg resin greater than the thermoplastic toughening agent of about 20 weight %.
5. prepreg composition as claimed in claim 1 is characterized in that, described prepreg resin is uniform basically composition.
6. prepreg composition as claimed in claim 1 is characterized in that described layer of fibers comprises carbon fiber.
7. prepreg composition as claimed in claim 1 is characterized in that described thermosetting resin is selected from Resins, epoxy, cyanate ester resin, polyamide resin and polyimide resin.
8. prepreg composition as claimed in claim 7, it is characterized in that, described Resins, epoxy is selected from the triglycidyl ether and the N of bisphenol-f-diglycidylether, bisphenol-A-diglycidylether, epoxy phenol phenolic varnish, cresol novolac epoxy varnish, p-aminophenol, N, N ', N '-four glycidyl group-4, the 4-methylenedianiline.
9. prepreg composition as claimed in claim 1 is characterized in that, described thermoplasticity viscosity modifier is selected from polyhydroxy ether, polyethersulfone, polyether ethersulfone, polyethersulfone/polyether ethersulfone multipolymer, polyvinyl butyral acetal and polyvinyl formal.
10. prepreg composition as claimed in claim 1 is characterized in that, described thermoplastic toughening agent is selected from polyethersulfone, polyether ethersulfone and their multipolymer.
11. one kind prepares the prepreg method for compositions, this method comprises:
Formation comprises the prepreg resin of thermosetting resin, solidifying agent, thermoplasticity viscosity modifier and thermoplastic toughening agent, wherein, gross weight in net phase prepreg resin sample is a benchmark, and the total content of thermoplasticity viscosity modifier and thermoplastic toughening agent is about 25-40 weight %; Be benchmark in thermoplasticity viscosity modifier and thermoplastic toughening agent gross weight separately, record respectively have the thermoplasticity viscosity modifier and the thermoplastic toughening agent that surpass 10 weight % to dissolve in the prepreg resin respectively at about 25 ℃; Be under 2 ℃/minute the condition, net phase prepreg resin sample to be recorded in heating rate, the minimal viscosity of prepreg resin is about the 25-1500 pool; And
Many fibers are contacted with the prepreg resin.
12. method as claimed in claim 11 is characterized in that, described prepreg resin comprises solvent.
13. method as claimed in claim 12 is characterized in that, described solvent is selected from acetone, 1,3-dioxolane, methyl ethyl ketone, methylene dichloride, tetrahydrofuran (THF) and dimethyl formamide.
14. method as claimed in claim 12 is characterized in that, this method also comprises the described solvent of evaporation.
15. method as claimed in claim 11 is characterized in that, described prepreg resin is uniform basically composition.
16. method as claimed in claim 11 is characterized in that, all basically thermoplasticity viscosity modifiers all dissolve in the prepreg resin.
17. method as claimed in claim 11 is characterized in that, dissolves in the prepreg resin greater than the thermoplastic toughening agent of about 20 weight %.
18. method as claimed in claim 11 is characterized in that, described thermosetting resin is selected from Resins, epoxy, cyanate ester resin, polymeric amide and polyimide.
19. method as claimed in claim 11, it is characterized in that described thermoplasticity viscosity modifier is selected from polyhydroxy ether, polyethers, polyethersulfone, polyether ethersulfone, polyethersulfone/polyether ethersulfone multipolymer, polysulphide, cresols phenolic varnish, phenol phenolic varnish, cresol novolac epoxy varnish, epoxy phenol phenolic varnish, polyvinyl butyral acetal, polyvinyl chloride, polyvinyl alcohol, polyvinyl acetate, polyvinyl formal, the rubber that contains vinyl cyanide and polyimide.
20. method as claimed in claim 11 is characterized in that, described thermoplastic toughening agent is selected from polyethersulfone, polyether ethersulfone and their multipolymer.
21. method as claimed in claim 11 is characterized in that, the formation of prepreg resin comprises:
Formation comprises the premixture of following component: the thermoplastic toughening agent of first part and at least a component that is selected from down group: at least a portion thermosetting resin, at least a portion solidifying agent and at least a portion thermoplasticity viscosity modifier, wherein, the thermoplastic toughening agent of all basically described first parts all dissolves in this premixture;
Described premixture is mixed with the thermoplastic toughening agent of second section at least.
22. method as claimed in claim 21 is characterized in that, this method is included in and forms described premixture under the temperature that is approximately higher than 40 ℃.
23. method as claimed in claim 21 is characterized in that, described second section thermoplastic toughening agent comprises the thermoplastic toughening agent particle that number average particle size is the 60-150 micron.
24. a composite structure, it comprises the matrix material that makes by the prepreg composition that solidifies claim 1.
25. composite structure as claimed in claim 24 is characterized in that, described composite structure is the form of honeycomb-like sandwich structure.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US57144904P | 2004-05-14 | 2004-05-14 | |
| US60/571,449 | 2004-05-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1954024A true CN1954024A (en) | 2007-04-25 |
Family
ID=35044894
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2005800152855A Pending CN1954024A (en) | 2004-05-14 | 2005-04-28 | Self-adhesive prepreg |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20060057331A1 (en) |
| EP (1) | EP1756206A2 (en) |
| JP (1) | JP2007537331A (en) |
| CN (1) | CN1954024A (en) |
| CA (1) | CA2566447A1 (en) |
| TW (1) | TW200609279A (en) |
| WO (1) | WO2005113652A2 (en) |
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| CN104059237A (en) * | 2013-03-19 | 2014-09-24 | 西门子公司 | Fiber Reinforced Plastic Composite, Method Of Manufacturing Thereof, Plastic Composite Starting Material For Manufacturing Fiber Reinforced Plastic Composite And Purposes |
| CN105672036A (en) * | 2015-12-22 | 2016-06-15 | 中国航空工业集团公司济南特种结构研究所 | Impregnation formula for punched Nomex paper honeycomb and use method thereof |
| TWI584947B (en) * | 2012-12-05 | 2017-06-01 | 塞特工業公司 | Conductive surfacing material for composite structures |
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| CN112166016A (en) * | 2018-04-04 | 2021-01-01 | 斯道拉恩索公司 | Method of making a dry-laid mat for thermoforming |
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| US7550190B2 (en) * | 2004-09-01 | 2009-06-23 | Hexcel Corporation | Rubber-modified edge coating for honeycomb used in panels with composite face sheets |
| DE102006035847B4 (en) * | 2006-08-01 | 2009-11-19 | Airbus Deutschland Gmbh | Structural arrangement and method for producing a component for aerospace |
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| WO2012046088A1 (en) * | 2009-10-07 | 2012-04-12 | Hexcel Composites, Ltd. | Thermosetting resin adhesive containing irradiated thermoplastic toughening agent |
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- 2005-04-28 CN CNA2005800152855A patent/CN1954024A/en active Pending
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- 2005-04-28 JP JP2007513175A patent/JP2007537331A/en active Pending
- 2005-04-28 WO PCT/US2005/014427 patent/WO2005113652A2/en not_active Application Discontinuation
- 2005-04-28 CA CA 2566447 patent/CA2566447A1/en not_active Abandoned
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2005113652A2 (en) | 2005-12-01 |
| US20060057331A1 (en) | 2006-03-16 |
| JP2007537331A (en) | 2007-12-20 |
| WO2005113652A3 (en) | 2006-02-02 |
| EP1756206A2 (en) | 2007-02-28 |
| CA2566447A1 (en) | 2005-12-01 |
| TW200609279A (en) | 2006-03-16 |
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